JP4191748B2 - Monomer polymerization process in fluidized bed. - Google Patents

Monomer polymerization process in fluidized bed. Download PDF

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JP4191748B2
JP4191748B2 JP2006126464A JP2006126464A JP4191748B2 JP 4191748 B2 JP4191748 B2 JP 4191748B2 JP 2006126464 A JP2006126464 A JP 2006126464A JP 2006126464 A JP2006126464 A JP 2006126464A JP 4191748 B2 JP4191748 B2 JP 4191748B2
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JP2006241467A (en
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グリフィン、ジョン・ロバート
ディチェリス、マーク・ルイス
ミュール、マイケル・エルロイ
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エクソンモービル・ケミカル・パテンツ・インク
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1809Controlling processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818Feeding of the fluidising gas
    • B01J8/1827Feeding of the fluidising gas the fluidising gas being a reactant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00265Part of all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2208/00274Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00584Controlling the density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00628Controlling the composition of the reactive mixture
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14Monomers containing five or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Description

FIELD OF THE INVENTION This invention relates to a continuous process for the gas phase polymerization of olefins in a fluid bed reactor. More particularly, the present invention relates to a gas phase polymerization process for polymerizing monomers in a fluidized bed reactor operated in a condensed mode. More specifically, the present invention relates to a condensation mode gas phase polymerization method using a bulky ligand transition metal compound as a catalyst.

BACKGROUND OF THE INVENTION It is well known that gas phase fluidized bed polymerization processes yield a wide variety of polymers. Such a process employs a continuous cycle, in which a circulating gas stream (also known as a recycle stream or fluidizing medium) is heated in the reactor by the heat of polymerization. This heat is removed in another part of the cycle by a cooling system external to the reactor.

  In a gas phase fluidized bed process for synthesizing polymers from monomers, a gas stream containing one or more monomers is generally passed through a fluidized bed in the presence of a catalyst under reactive conditions. Circulate continuously. This gas stream is recovered from the fluidized bed and recycled back to the reactor. At the same time, the product polymer is withdrawn from the reactor and new (ie fresh) monomer is added instead of polymerized monomer.

  Over the past long time, it has not been possible to lower the temperature of the recycle stream introduced into the reactor below the dew point of the recycle stream. The dew point of the recycle stream is the temperature at which liquid condensate begins to form in the gas recycle stream. In later years, as disclosed in US Pat. Nos. 4,543,399 and 4,588,790 to Jenkins, III et al., The recycled stream was cooled to a temperature below the dew point in a fluidized bed polymerization process to condense a portion of the recycled stream. It has been demonstrated that The recycle stream entrained with liquid droplets thus obtained is returned to the reactor. The contents of Jenkins, III et al. U.S. Pat. Nos. 4,543,399 and 4,588,790 are all incorporated herein by reference. For purposes of this patent application, a recycle stream having a liquid and a gas phase is intentionally introduced to the reactor such that the weight percent of the liquid, based on the total weight of the recycle stream, exceeds about 2.0 weight percent. The process introduced is defined as operating the gas phase polymerization process in “condensed mode”.

The catalyst system described by Jenkins, III et al. Is a traditional Ziegler-Natta catalyst system based on TiCl 3 . Use of such a catalyst system for condensed mode operation inevitably results in process and product constraints, as will become apparent from the subsequent description herein. Such process constraints limit the production rate and significantly increase the production cost of the polymer. Also, as a direct consequence of using such traditional catalysts in this process, the polymers that can be produced are limited to those of a certain density and melt index.

  The production rate and properties of the polymer can be controlled to give the desired melt index and density in the gas phase fluidized bed reactor. In the operation of a gas phase fluidized bed reactor, such a process is a closed system. Changing one or more reactor conditions in the process can be accompanied by indirect changes somewhere in the closed system. Therefore, great care must be taken to avoid conditions that can cause chunking, sheeting, fluid bed collapse, reaction shutdown and reactor shutdown.

  With respect to operating temperature, comonomer (group) to monomer ratio, and hydrogen to monomer ratio, there are target values determined by the polymer and catalyst to be produced. In traditional catalyst systems and polymers produced with such catalyst systems, these target values are constrained and the direct consequence is that the production rate that can be achieved in producing a given polymer is drastically reduced. In addition, these traditional catalysts and catalyst systems limit the type and properties of the polymer.

  Accordingly, there is a need for a gas phase polymerization process that can expand the previously constrained target value. If such a target value could be expanded beyond the range that could be achieved previously, the gas-phase fluidized bed polymerization reactor could be operated at a significantly higher production rate and could not be realized in the past. Various grades of polymers can be produced at significantly reduced costs.

SUMMARY OF THE INVENTION The present invention is a continuous gas phase for polymerizing α-olefins in a gas phase fluidized bed reactor operated in a condensed mode utilizing a bulky ligand transition metal compound such as a metallocene. The present invention relates to a phase polymerization method.

The present invention, in another embodiment, relates to a continuous process for polymerizing an α-olefin monomer and at least one copolymerizable α-olefin comonomer in a gas phase fluidized bed reactor. The recycle stream is (C X + H 2 ) / C y with a ratio of less than about 0.2, a dew point increasing component in an amount of 21.1 mol% or more, and a non-condensable inert that forms the remainder of the recycle stream Pass through the reactor so as to comprise the components. However, C X , H 2 and Cy are respectively mol% of comonomer, hydrogen and monomer. A catalyst is introduced into the reactor under reactive conditions, the recycle stream is polymerized into a polymer product, and the resulting polymer is withdrawn from the reactor. A recycle stream containing unreacted monomers is also recovered from the reactor and additional monomer is introduced into the recycle stream in place of the polymerized monomer so that the above ratio of recycle stream is maintained. In a preferred embodiment, the recycle stream is compressed and / or cooled to produce a liquid phase and a gas phase, which are reintroduced into the reactor.

In a preferred embodiment, the α-olefin is ethylene. In another preferred embodiment, the comonomer is a C 5 or higher (ie higher carbon number) α-olefin.
One object of the present invention is to provide a process for polymerizing olefins at a significantly higher production rate in a gas phase fluidized bed polymerization reactor. Another object of the present invention in this regard is to provide a process that results in an increased cooling capacity of the recycle stream. It is another related object of the present invention to provide a polymerization process for producing polymers having a wider range of density and melt index than before. It is also an object of the present invention to provide a process that can further reduce energy, raw materials and capital expenditure.

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a gas phase polymerization process for polymerizing olefins utilizing metallocene in a gas phase fluidized bed polymerization reactor operated in a condensed mode. The present invention significantly increases the production rate of the polymer produced in the gas phase fluidized bed reactor. The present invention further allows the production of a wide range of polymers with improved properties under such significantly higher production rates. Traditional Ziegler-Natta catalysts are generally insoluble in hydrocarbon solvents. For example, traditional Ziegler-Natta catalysts are typically isolated by precipitation in a hydrocarbon solvent such as isopentane. Surprisingly, the metallocene catalyst was soluble in hydrocarbon solvents, but polymerized olefins in a condensation mode process utilizing hydrocarbon solvents as the preferred condensable inert component.

  The present invention relates to a gas phase polymerization or copolymerization reaction involving the polymerization of one or more α-olefin monomers having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms. The present invention is particularly suitable for copolymerization reactions involving the polymerization of one or more monomers.

  Monomers include, for example, α-olefin monomers such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, and styrene. It is a cyclic olefin. Other monomers include polar vinyl, dienes, norbornene, acetylene and aldehyde monomers. Preferably, a copolymer of ethylene is produced in which the amount of ethylene and comonomer is adjusted to yield the desired polymer product. Preferably, the comonomer is an α-olefin having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. In another embodiment, ethylene is polymerized with at least two comonomers to form a terpolymer or the like.

  Catalysts useful in the polymerization process of the present invention generally belong to the field of transition metal catalysts and include many metal-organic transition metals. During the past few years, new catalyst technologies have been developed that allow the properties and properties of the polymer to be adjusted and / or controlled. This technique mainly involves the use of a single site catalyst (single active site catalyst) and generally results in a wide range of polymers having a narrow molecular weight distribution and a narrow composition distribution. This technology has so far focused on the type of catalyst and catalyst system used and the attributes of the products produced therein, but obtained when these catalysts are used in a condensed mode gas phase polymerization process. Numerous surprising and surprising benefits have not been recognized.

  Certain metal-organic catalysts and catalyst systems are suitable for the synthesis of polymers from certain gaseous compositions that are introduced into the reactor as a recycle stream. As for the catalyst, a bulky ligand transition metal catalyst is preferred. The bulky ligand contains multiple linking atoms (preferably carbon atoms) to form an atomic group that can form a ring (possibly with one or more heteroatoms). . The bulky ligand may be a cyclopentadienyl derivative, which may be mononuclear or polynuclear. One or more bulky ligands can be bound to the transition metal atom. The transition metal atom is a group IV, group V or group VI transition metal of the periodic table. Other ligands may be bonded to the transition metal, but those that can be eliminated as a hydrocarbyl or halogen leaving group by a cocatalyst are preferred. The catalyst can be derived from a compound represented by the following formula:

[L] m M [X] n where L is a bulky ligand, X is a leaving group, M is a transition metal, and m and n are the sum of the ligand valences. The number is equal to the transition metal valence. Preferably, the catalyst is tetracoordinate so that the compound can be ionized to the 1+ valence state.

  The ligands L and X may be bridged with each other, and when two ligands L and / or X are present, they may be bridged between them. The metallocene may be a complete sandwich compound having two ligands L, both of which are cyclopentadienyl groups, or it may have only one ligand L, which is cyclopentadienyl. It may be a half-sandwich compound.

  Certain metallocenes have the properties required for the process of the present invention.

For purposes of this specification, the term “metallocene” is defined as including one or more cyclopentadienyl moieties along with transition metals of the Periodic Table of Elements. The metallocene catalyst component is represented by the general formula (Cp) m MR n R ′ p . Where Cp is a substituted or unsubstituted cyclopentadienyl ring, M is a Group IV, Group V or Group VI transition metal, and R and R ′ are each independently a halogen, hydrocarbyl group or The hydrocarbyloxy group having 1 to 20 carbon atoms is selected from m = 1 to 3, n = 0 to 3, p = 0 to 3, and the sum of m + n + p is equal to the oxidation state of M. Various metallocene type catalyst systems can be used in the polymerization process of the present invention. Examples of the development of such metallocene catalysts for ethylene polymerization can be found in Ewen et al. US Pat. No. 4,937,299 and European Patent Application Publication No. 0129368, published July 26, 1989. All of these disclosures are incorporated herein by reference in their entirety. These publications teach the structure of various metallocene catalysts, including alumoxane as a cocatalyst. There are various methods for producing alumoxane, one of which is described in US Pat. No. 4,665,208. Cocatalysts other than alumoxane can also be used with the metallocene. Specific examples thereof are trialkylaluminum compounds or ionic activators or compounds having an ionizing action, such as tri (n-butyl) ammonium tetra (pentafluorophenyl) boron. Tri (n-butyl) ammonium tetra (pentafluorophenyl) boron ionizes the neutral metallocene compound. Such an ionizing compound may contain active protons, or may coordinate at all or only moderately to the remaining ions of other cations that have the ionizing action. It may contain cations that are associated in a state. Such compounds are described in EP-A-0277703 and 0277704, published Aug. 3, 1988. All of these disclosures are incorporated herein by reference in their entirety. Further, the metallocene catalyst component may be a monocyclopentadienyl-containing heteroatom compound. This heteroatom is activated with either an alumoxane or an ionic activator to yield an active polymerization catalyst system for the production of polymers useful in the present invention. Such types of catalyst systems are described in PCT International Publication No. WO 92/00333, published on January 9, 1992, US Pat. Nos. 5,096,867 and 5,055,438, European Patent Application Publication No. 0420436, International Publication No. WO 91/04257. Has been. All of these disclosures are incorporated herein by reference in their entirety. In addition, the metallocene catalysts useful in the present invention may include non-cyclopentadienyl catalyst components or secondary ligands such as boroles and carbollides with transition metals. Further, even if the catalyst and catalyst system are those described in US Pat. No. 5,064,802, PCT International Publications WO 93/08221 and WO 93/08199 published on April 29, 1993, they are within the scope of the present invention. . All of these disclosures are incorporated herein by reference in their entirety. All of the above catalyst systems may be prepolymerized, if desired, or used in combination with an additive component or scavenger component to improve catalyst productivity.

  It is preferred to select a metallocene that has a good comonomer incorporation rate, hydrogen sensitivity and polymerization activity. Preferred metallocenes are those having two or more substituents on at least one cyclopentadienyl group, for example mono- or bis-substituted cyclopentadienyl zirconocenes, in particular bis (1-methyl, 3-n-butylcyclopenta). Dienyl) zirconium dichloride. Metallocene catalysts that are too hydrogen sensitive or generate hydrogen can limit the process for producing high melt index materials. If the activity is too low, not only will the amount of ash increase, but a high level of stabilizer will be required. If the activity is too high, there is a possibility of causing contamination by deposits. If the comonomer incorporation rate is too low, it can adversely affect the manufacturable range of low density materials. By adjusting the composition of the feed gas stream (ie, the recycle stream) depending on the type of metallocene, a broad product range can be obtained. A mixture of two or more different metallocenes can also be used.

  The catalyst may be supported on a suitable particulate material such as a polymeric support or an inorganic oxide such as silica, alumina or mixtures thereof. US Pat. Nos. 4,808,561, 4,897,455, 4,937,301, 4,937,217, 4,912,075, 5,0008228, 5,086025, and 5,147,949 have been disclosed as methods for supporting the catalyst of the present invention. And U.S. Patent Application No. 898255 filed June 15, 1992 and U.S. Patent Application No. 885170 filed May 18, 1992. All of these disclosures are incorporated herein by reference in their entirety. Preferred loading methods are comprehensively disclosed in the aforementioned U.S. Pat. No. 4,937,301 and related U.S. patents.

How much polymer density results from a level of comonomer depends on how much comonomer the catalyst incorporates. For example, a catalyst with a high incorporation rate can produce a low density polymer with a low level of comonomer. Similarly, how much melt index is obtained depends on how much the catalyst reacts with hydrogen. For ethylene, the preferred α-olefin monomer, depending on the catalyst, the density ranges from about 0.86 g / cm 3 to about 0.96 g / cm 3 , preferably from about 0.88 g / cm 3 to about 0.94 g. C x / C 2 ratio is preferably less than about 0.2, more preferably to give a polymer of / cm 3 , most preferably from about 0.90 g / cm 3 to about 0.935 g / cm 3. Less than about 0.1 and as low as about 0.02.

  The advantages and benefits obtained with the present invention are similar for polymers having a melt index of greater than or equal to about 0.05 dg / min and less than about 1000 dg / min, preferably less than about 100 dg / min. Be found.

Ethylene is the preferred monomer, depending on the catalyst, but the melt index ranges from about 0.05 dg / min to about 1000 dg / min, preferably from about 0.05 dg / min to about 100 dg / min, more preferably about The H 2 / C 2 ratio is less than about 10,000 ppm, preferably less than about 5000 ppm, more preferably less than about 1000 ppm to give a polymer of 0.1 dg / min or more, most preferably about 0.5 dg / min or more. Most preferably, it is less than 500 ppm.

The reactivity ratio of the catalyst and catalyst system of the present invention is generally less than about 2, preferably less than about 1. The reactivity ratio is defined as the comonomer to monomer molar ratio (C x / C y ) in the recycle stream divided by the comonomer to monomer molar ratio (C x / C y ) in the resulting polymer. that (although, C x is the mole% comonomer, C y is the mole percent of the monomers). The catalyst useful in the present invention preferably has a productivity greater than 2000 g polymer / g catalyst, preferably greater than about 3000 g polymer / g catalyst, and most preferably about 3500 g polymer / g catalyst. Productivity exceeding. Productivity is affected by ethylene partial pressure. The preferred mole percent of ethylene is from about 25 to about 75 mole percent and the monomer partial pressure is from about 75 psia (517 kPaa) to about 240 psia (1655 kPaa). It is desirable that the catalyst efficiently connects the monomers so that the amount of ash is low.

In a preferred embodiment, the composition of the recycle stream used for fluidizing the catalyst bed in the reactor is such that the (C x + H 2 ) / C y ratio is less than about 0.2, preferably less than about 0.1. maintained at (although, C x, H 2 and C y are each comonomer, the molar% of the hydrogen and monomer). The recycle stream also contains dew point increasing components in the range of about 2.0 to about 6.0 mol%, and the amount of dew point increasing components is preferably about 2.5 mol% or more, more preferably about 5. Although it is 0 mol% or more, it does not exceed the amount that would destroy the fluid state. In a preferred embodiment, the remaining components of the recycle stream consist of non-condensable inert components such as nitrogen (N 2 ). The preferred α-olefin is ethylene and the preferred comonomer is pentene-1, hexene-1 or octene-1.

  Combining the above-described catalyst with a recycle stream composition makes it possible to achieve high reactor productivity for lower density or higher melt index copolymers. The process of the present invention requires significantly less comonomer and hydrogen and greatly increases the cooling capacity of the recycle stream. The increase in productivity is due to an improvement in the cooling capacity (also referred to as cooling capacity) of the recycle stream having the above recycle stream composition of the process of the present invention. This is associated with an increase in the gas density of the recycle stream and a change in the specific enthalpy of the recycle stream (also referred to as a change in specific enthalpy when moving from inlet conditions to reactor conditions).

  The closer the dew point is to the reactor temperature, the greater the possibility that the polymers will stick together. Adhesion can also be caused by fusion of polymer particles at reactor temperatures that are too high. When sticking between polymers occurs, instability may be brought about in the fluidized state. This causes chunking and makes downstream operations such as extrusion more difficult. There is no generally accepted view on what causes chunking and seating. Apparently, some form of fusion between the polymer particles is involved, probably due to inadequate fluidization in the fluidized bed resulting in insufficient heat transfer. It is.

  However, no clear correlation has been found so far between the settings and measurements of individual processes and the occurrence of chunking and sheeting. However, in a preferred embodiment, it is best to maintain the temperature difference between the dew point temperature and the reactor temperature above about 5 ° F. (2.8 ° C.), and in a more preferred embodiment the temperature difference is about 10 ° F. Maintain above (5.6 ° C).

  Also, as a direct result of the reduced comonomer amount in the process of the present invention, a wide range of density and melt index range polymers can be produced efficiently and cost-effectively. With the process of the present invention, relatively high reactor temperatures can be used, which not only favors catalyst activity, but also increases reactor productivity due to high levels of cooling. Combining a reduction in comonomer amount, a reduction in the overall amount of polymerization reactants, and a high reactor temperature can provide significant improvements to the process.

  A high reactor temperature is believed to be accompanied by a decrease in the adhesion of the polymer particles in the fluidized bed as a result of a decrease in the amount of low molecular weight amorphous material produced and a decrease in the amount of dissolved comonomer in the polymer. The decrease in adhesiveness improves the fluidity of the resin and facilitates downstream handling.

  Preferably, the selection of the catalyst is performed such that the hexane extract is less than about 2 wt%, preferably less than about 1 wt%. The hexane extract can be determined in detail by citing 21 CFR 177.1520 (d) (3) (ii). The choice of catalyst is preferably made so that the composition distribution width index (CDBI) of the polymer is greater than 50%, preferably greater than 60%, most preferably in the range of 60% to about 80%. CDBI and its measurement and calculation methods are described in detail in PCT application WO 93/03093 published on February 18, 1993. Basically, CDBI is a measure of composition distribution. CDBI is defined as the weight percent of a copolymer having a comonomer content within 50% of the median total comonomer molar content (ie, within 25% on either side of the median). The

  The reduction in tack also appears as an improvement in the production capacity of the high melt index or low density polymer in the present invention. In addition, due to the decrease in tackiness, the reactor temperature can be significantly increased from that which could be achieved in the past, and higher cooling capacity can be achieved.

The term “dew point increasing component” is used in the present specification to exclude a polymerizable monomer and to include a component that increases the dew point. For purposes of this specification, the term “dew point raising component” includes saturated or non-polymerizable unsaturated hydrocarbons. A specific example of a suitable dew point increasing component is a readily volatile liquid hydrocarbon, which can be selected from saturated hydrocarbons having 3 to 10 carbon atoms. Taking Some suitable saturated hydrocarbons, propane, n- butane, isobutane, n- pentane, isopentane, neopentane, n- hexane, isohexane and other saturated C 6 hydrocarbons, n- heptane, and n- octane Other saturated C 7 and C 8 hydrocarbons, or mixtures thereof.

Preferred hydrocarbons are C 4 -C 6 saturated hydrocarbons. Preferred dew point increasing components are pentanes. Preferably, the recycle stream contains from about 5 to about 60 mole percent dew point increasing component, preferably the component is one less carbon than comonomer or one or more carbons less than comonomer. This helps to achieve high reactor productivity. The dew point itself is calculated from the composition of the supply gas analyzed by, for example, gas chromatography. Combining this with the actual recycle gas temperature and pressure also calculates the weight percent of condensate in the recycle stream.

  A preferred method of measuring fluid bed stability is to monitor fluid bulk density, measure pressure in the upper portion of the fluid bed, or detect the formation of chunks in the reactor. The flow bulk density (FBD) is the ratio of the pressure drop upward of a given portion in the center of the reactor to the height of that given portion. It should be understood that under certain conditions known to those skilled in the art, the measured average value may be higher or lower than the actual catalyst bed bulk density. Fluid bed stability is affected by specific operating conditions, but it is difficult to relate them. In general, the operating temperature should be below the melting point and should be below the temperature at which the particles begin to show tackiness as described above. Using the present invention, a high reactor temperature can be maintained at a low density, high melt index using higher olefin comonomer and high concentration dew point increasing component. In a preferred embodiment, it is important that so much condensable component should not be added that the dew point is increased such that the degree of evaporation in the reactor is insufficient. Applicants have found that it is important to maintain the ratio of FBD to sediment volume density above 0.59 when increasing the concentration of condensable components in the airflow passing through the catalyst bed.

  In the practice of the present invention, the weight percent of liquid in the recycle stream (based on the total weight of the recycle stream) is in the range of about 2 to about 50 weight percent, preferably about 10 weight percent or more, more preferably about 15 weight percent. % By weight, more preferably about 20% by weight or more, most preferably in the range of about 25% to about 40% by weight.

  In a preferred embodiment of the present invention, recycling is performed so that the flow of the recycle stream is uniform and the fluidized bed is maintained in a floating state, and the uniformity of the recycle stream passing upward through the entire fluidized bed is ensured. The point of introduction of the stream is preferably located below the fluidized bed. In another embodiment of the invention, the recycle stream can be divided into two or more separate streams, one or more of which can be introduced directly into the fluidized bed, provided that the bottom of the fluidized bed and The condition is that the gas velocity passing through the fluidized bed is large enough to keep the fluidized bed floating. For example, the recycle stream can be divided into a liquid stream and a gas stream, which can be introduced separately into the reactor.

  The reactor pressure can vary from about 100 psig (689.7 kPag) to about 500 psig (3448.3 kPag), but is preferably in the range of about 200 psig (1379.3 kPag) to about 400 psig (2758.6 kPag), most preferably. Within the range of about 250 psig (1724.1 kPag) to about 350 psig (2413.8 kPag). Combining increased catalytic activity with good comonomer incorporation rate and hydrogen sensitivity can reduce total pressure or ethylene partial pressure. Typical reactor temperatures are in the range of about 130 ° F. (54.4 ° C.) to about 250 ° F. (121.1 ° C.), but preferably about 140 ° F. (60 ° C.) to about 220 ° F. (104.4 ° C.), more preferably in the range of about 145 ° F. (60.7 ° C.) to about 215 ° F. (101.7 ° C.), more preferably about 155 ° F. (68.3 ° C.). To about 200 ° F. (93.3 ° C.), most preferably in the range of about 165 ° F. (73.9 ° C.) to about 185 ° F. (85 ° C.). The temperature difference between the dew point temperature and the inlet temperature is preferably less than 40 ° C, preferably less than 30 ° C, more preferably less than 20 ° C, most preferably between 5 ° C (preferably 10 ° C) and about 15 ° C. is there. The apparent flow velocity of the gas stream passing through the reactor generally exceeds the minimum flow rate required for fluidization, but such minimum flow rate is typically about 0.2 ft / sec (0.061 m / s) to 0. 0.5 ft / sec (0.153 m / s). The apparent air velocity is preferably kept so as not to fall below 0.7 ft / sec (0.214 m / s), and more preferably kept so as not to fall below 1.0 ft / sec (0.305 m / s). The apparent air velocity should preferably not exceed 5.0 ft / sec (1.5 m / s).

  The following examples are provided for a better understanding of the present invention, including its typical advantages and limitations.

Example 1
Various catalysts were used in the examples. In the field control test C-1 and extrapolation data test C-1A in Table 1, a titanium-based catalyst similar to the catalyst described in US Pat. No. 4,543,399 was used. The catalyst used was a complex of tetrahydrofuran, magnesium chloride and titanium chloride with diethylaluminum chloride (diethylaluminum chloride / tetrahydrofuran molar ratio = 0.4) and tri-n-hexylaluminum (trin-hexylaluminum / tetrahydrofuran molar ratio = 0.28) and impregnated with silicon dioxide treated with triethylaluminum. The activator is triethylaluminum (TEAL).

  In field tests 2A and 8A in Table 3 and extrapolation data tests 2-6 in Table 1, tests 8-13 in Table 3, tests 14-18 in Table 4, the catalyst is a disubstituted cyclopentadienyl ring described below. It was a metallocene with

To a clean dry N 2 mixer was added 800 g of silica with a LOI (OH content) of about 3 wt% dehydrated at 200 ° C., and 2000 ml of toluene was quickly added to the container. While stirring, 1060 ml of 30 wt% MAO based on the Al content was added to this container. The jacket temperature was raised so that the temperature in the container was 155 ° F. The mixture was maintained at this temperature for 4 hours under stirring. Thereafter, 23 g of bis (1-methyl, 3-n-butylCp) ZrCl 2 dissolved in about 500 ml of toluene was quickly added to the reaction vessel with stirring. While continuing to stir, the reactor temperature was again maintained at 155 ° F for 1 hour. Finally, the catalyst solids were dried by blowing nitrogen at 155 ° F. under vacuum until the solids became free-flowing and less than 10% by weight of volatiles.

  The catalyst used in the implementation test 7A of Table 3 and the extrapolation data test 7 of Table 1 was prepared as follows.

  All steps were performed in a dry box using a dry degassed solvent. Thus, to a clean dry 1 l round bottom flask was added 300 ml of a 25 wt% triethylaluminum solution dissolved in heptane. 300 g of silica dehydrated at 800 ° C. was added with stirring over 15 minutes. The silica was Davison 948. The solvent was removed under vacuum to obtain a free-flowing solid. While stirring in a 2 l round bottom flask, 12.0 g of dimethylaluminum salt of tetraxperfluorophenyl boron was dissolved in 800 ml of hot (100 ° C.) toluene. This solution was passed through a cannula into a 3 liter round bottom flask in which 300 g of TEAL-treated silica prepared as described above was suspended in 500 ml of hot (100 ° C.) toluene with a mechanical overhead stirrer. The mixture was allowed to cool to room temperature and 1200 ml of pentane was added while stirring with a mechanical overhead stirrer. The solvent was decanted and the remaining solvent was removed under vacuum to give a free-flowing solid.

  The supported activator prepared above was suspended in 500 ml of pentane and then 5.43 g of bis (n-butylcyclopentadienyl) dimethylzirconium dissolved in 200 ml of pentane was added. The solvent was decanted and the remaining solvent was removed under vacuum to give a free-flowing solid.

  Test C-1 in Table 1 and Tests 2A, 7A and 8A in Table 3 are based on field tests. Tests C-1A and 2-7 in Table 1, Tests 8-13 in Table 2, and Tests 14-18 in Table 4 provide information obtained from field operations to estimate various field conditions and production rates. Obtained by extrapolation using known thermodynamic equations.

Test C-1
Test C-1 in Table 1 is measured data obtained at the plant and the process and catalyst system are substantially the same as those disclosed in US Pat. Nos. 4,543,399 and 4,588,790.

Test C-1A
Test C-1A in Table 1 includes data extrapolated from test C-1 above. This test illustrates that the preferred dew point limit has been reached for this particular grade of material. The limit is that the difference between the reactor temperature and the dew point temperature is about 10 ° F. (5.6 ° C.). At this point, further raising the dew point closer to the reactor temperature leads to fluid bed destabilization, possibly leading to seating and chunking.

Test 2 and 2A
Test 2 in Table 1 includes data extrapolated from Test 2A in Table 3. Test 2A is actual measurement data obtained in a pilot plant. Test 2 shows the corresponding data when this data is scaled up to the reactor used in Test C-1. The catalyst used has already been described above. As can be seen from the table, the C x / C 2 ratio and the H 2 / C 2 ratio are significantly lower than in tests C-1 and C-1A.

Test 3-6
Test 3-6 shows the extrapolated data when increasing the amount of (isopentane (i-C 5) using in this example) the dew point elevated components in the recycle stream composition. The amount of i-C 5 was increased from 1.6 mol% in Test 2 to 21.1 mol% in Test 6. Then, the dew point steadily increases and reaches the dew point limit of 10 ° F. (5.6 ° C.), but the production rate for the same polymer grade increases dramatically. That number is significantly above the limit of test C-1A. Note that the reactor and inlet temperature, pressure and gas velocity are constant. It should also be noted that in tests that illustrate the process of the present invention, the gas density is much higher, as is the enthalpy change of the circulating gas. If the reactor temperature is increased to 186 ° F (85 ° C) and the dew point is increased to 174.7 ° F (79.3 ° C), the production rate is further increased to 167,000 lb / hr (76.0 t / hr). Can do.

Tests 7 and 7A
Test 7 in Table 1 includes data extrapolated from actually measured data obtained in the pilot plant shown in Test 7A in Table 3. The catalyst system was changed as described above. As the results show, production rates can be increased with different metallocene catalyst systems.

Test 8-13
Test 8 includes data extrapolated from actually measured data obtained in the pilot plant shown in Test 8A of Table 3. The catalyst system used is identical to tests 2-6 in Table 1. However, the comonomer in tests 8 and 8A is octene-1.
Again, as the amount of dew point increasing component is increased, the production rate steadily increases and the production rate at the preferred dew point limit is 103400 lb / hr (47.0 t / hr).

The range of polymers that could be obtained in the past has been limited. At densities below 0.910 g / cm 3 , the polymer particles in the reactor begin to become sticky and the reactor temperature needs to be lowered, and the same is true for polymers with a density above 0.910 g / cm 3. Even for the particles, a melt index above about 100 dg / min (preferably above about 200 dg / min) further limits the range of addition of dew point raising components, resulting in reduced reactor production rates. Of course, it is possible to lower the ethylene partial pressure in order to compensate for the decrease in the production rate, but in this case, the catalytic activity is lowered due to the influence of the lower ethylene partial pressure. Attempting to increase the melt index encounters similar constraints.

Example 2
Table 4 is referred to here. Test 14 is measured data obtained in a plant employing a condensation mode process with a metallocene catalyst prepared from 200 ° C. silica having a moisture content of 4.1% by weight. This catalyst was prepared as follows. 229 pounds of silica was mixed with 310 pounds of a 30 wt% toluene solution of methylalumoxane. An additional 450 pounds of toluene was added and the mixture was maintained at 146 ° F. for 2 hours, after which 6.20 pounds of bis (n-butylcyclopentadienyl) zirconium dichloride was added and mixed for 1 hour. The catalyst was decanted and the solvent was changed several times with hexane. This was dried at 150 ° F. to obtain a free-flowing powder. The final catalyst weight was 340 pounds. This final catalyst sample had a zirconium loading of 0.37% and an aluminum loading of 12.5%.

Example 3
Although Table 5 is referred to here, tests 15 to 19 are extrapolated data. The same catalyst and settings as in Test 2 of Example 1 were used. This example illustrates the effect of certain specific dew point raising components. Various ingredients were used to raise the dew point to a temperature 10 ° F. (5.6 ° C.) below the reactor temperature. The cooling capacity and reactor productivity of these recycle streams were compared. It can be seen that lower molecular weight condensable hydrocarbons tend to increase reactor production rates. This may also be related to the low solubility of such hydrocarbons in the polymer particles, which may adversely affect fluid bed stability at high reactor temperatures. Has little effect on the melting point.

Although the invention has been described and illustrated with reference to specific embodiments thereof, those skilled in the art will recognize that the invention is suitable for making various changes and is not necessarily limited to that illustrated here. Should be understood. For example, it is within the scope of the present invention to reduce the temperature of the recycle stream using a cooling device or to operate two or more reactors in series with the same or different catalysts. For these reasons, reference should be made solely to the appended claims in defining the scope of the present invention.

Claims (31)

  1. A recycle stream having a liquid phase and a gas phase is converted into a recycle stream using a continuous gas phase polymerization process for polymerizing one or more α-olefins using a metallocene catalyst in a gas phase fluidized bed reactor. Introducing into the reactor such that the weight percent of the liquid, based on the total weight of the product, exceeds 2.0 weight percent, and the recycle stream comprises a dew point increasing component in an amount of 21.1 mol% or more. A method characterized by.
  2. The method of claim 1, wherein, wherein the recycled stream passing through the fluidized bed of the reactor contains a 21.1 to 60 mole% of the amount of dew point increasing component.
  3.   3. The method according to claim 2, wherein the dew point increasing component has one or more carbon atoms less than the α-olefin monomer having the highest carbon number in the recycle stream.
  4. 3. The method of claim 2, wherein the recycle stream contains a comonomer.
  5. The method of claim 4, wherein, the method C x / C y ratio (C x and C y are the a mole percent of comonomer and monomer respectively), characterized in that it is kept below 0.2.
  6. 6. A method as claimed in claim 4 or claim 5, wherein the recycle stream contains from 21.1 to 40 mol% dew point increasing components.
  7. In claims 3 to any one claims wherein the method of claim 6, wherein the containing the recycle stream further H 2 / C y molar ratio of less than 0.01 hydrogen (H 2) .
  8. The method of claim 7, wherein in that the recycle stream is in an amount of 10 mol ppm~10000 mol ppm hydrogen (H 2).
  9. The method of any one claims of claims 4 to claim 8, wherein the a composition of the recycle stream (C X + H 2) / C y ratio to less than 0.2.
  10. The method according to claim 9, wherein the a composition of the recycle stream (C X + H 2) / C y ratio to less than 0.1.
  11.   11. A method according to any one of claims 1 to 10, characterized in that the weight percentage of the liquid based on the total weight of the recycle stream is not less than 2.5 weight%.
  12.   12. A method according to claim 11, wherein the weight percentage of the liquid, based on the total weight of the recycle stream, is 5% to 50% by weight.
  13.   13. A method according to any one of claims 1 to 12, wherein the metallocene catalyst provides a reactivity ratio of less than 2.
  14.   14. The method according to any one of claims 1 to 13, wherein the productivity of the metallocene catalyst exceeds 2000 g polymer per g of the catalyst.
  15.   15. The method according to any one of claims 1 to 14, wherein the mol% of the α-olefin monomer is 10 to 90 mol%.
  16.   The method according to claim 15, wherein the α-olefin monomer has a mol% of 20 to 80 mol%.
  17.   The method according to claim 15 or 16, wherein the partial pressure of the α-olefin monomer is 70 psia (482.8 kPaa) to 240 psia (1655.2 kPaa).
  18.   18. A method according to any one of claims 15 to 17, characterized in that the recycle stream further comprises nitrogen in an amount of 5 to 50 mol%.
  19. The method of any one claims of claims 15 to claim 17, the polymer product, CDBI greater than 50%, the density and 0 in the range of 0.850g / cm 3 ~0.970g / cm 3 Having at least one melt index of greater than or equal to 0.01 dg / min and less than 1000 dg / min.
  20. 20. The method according to any one of claims 3 to 19, wherein the at least two α-olefin monomers are C 4 and C 2 α-olefins in a ratio of 0.001 to 0.2. Or the at least two α-olefin monomers are C 5 and C 2 α-olefin in a ratio of 0.001 to 0.15, or the at least two α-olefin monomers are 0 C 6 and C 2 α-olefins in a ratio of 0.001 to 0.1, or C 8 and C 2 α in a ratio of 0.001 to 0.05 A process characterized in that it is an olefin;
  21. A continuous process for polymerizing at least one copolymerizable α-olefin comonomer with ethylene in a gas phase fluidized bed reactor operated in a condensed mode, the process comprising the following steps:
    a) Stage of circulating a recycle stream through the fluidized bed in the reactor, wherein the recycle stream contains C x / C 2 in a ratio of less than 0.2 and a dew point increasing component in an amount of 21.1 mol% or more. Comprising (C x and C 2 are the mole% of comonomer and ethylene, respectively);
    b) introducing a metallocene catalyst into the reactor under reactive conditions to polymerize the recycled stream into a polymer product;
    c) recovering the recycle stream containing unreacted monomers from the reactor;
    d) introducing additional monomers into the recycle stream instead of polymerized monomers so that the ratio of the recycle stream is maintained;
    e) reintroducing the recycle stream into the reactor; and f) removing the polymer product from the reactor.
  22.   The method according to claim 21, wherein the α-olefin comonomer has 3 to 15 carbon atoms.
  23. According to claim 21 or claim 22 the method described in method characterized by the recycle stream comprises a C x / C 2 ratio of less than 0.1 in step a).
  24.   24. A method according to any one of claims 21 to 23, wherein the recycle stream comprises a non-condensable inert component.
  25.   25. The method according to any one of claims 21 to 24, wherein the metallocene catalyst is used with an alumoxane or an ionic activated complex.
  26. 26. The method according to any one of claims 21 to 25, wherein the comonomer is hexene-1 and the metallocene catalyst provides a reactivity ratio of less than 2, and wherein the polymer product is or density and melt index in the range of 0.88g / cm 3 ~0.970g / cm 3 is 0.1dg / min~1000dg / min, or the metallocene catalyst said comonomer is an octene-1 is 1 less and is to be given the reactivity ratios, yet melt index in the range density of 0.88g / cm 3 ~0.970g / cm 3 of the polymer product at 0.1dg / min~1000dg / min A method characterized by being.
  27. The method of any one claims of claims 21 to claim 26, a method of molar ratio of H 2 / C 2 is equal to or less than 0.01.
  28. A continuous process for polymerizing at least one copolymerizable α-olefin comonomer with ethylene in a gas phase fluidized bed reactor, the process comprising the following steps:
    a) circulating a recycle stream through the reactor, wherein the recycle stream is (C x + H 2 ) / C 2 in a ratio of less than 0.2, a dew point increasing component in an amount of 21.1 mol% or more, and Comprising the non-condensable inert components that make up the remainder of the recycle stream (C x , H 2 and C 2 are respectively mol% of comonomer, hydrogen and ethylene);
    b) introducing a metallocene catalyst system into the reactor under reactive conditions to polymerize the recycle stream into a polymer product;
    c) recovering the recycle stream containing unreacted monomers from the reactor;
    d) Compressing and cooling the recycle stream to produce a liquid phase and a gas phase such that the liquid weight percent exceeds 2.0 weight percent based on the total weight of the recycle stream, and reacting the recycle stream. Re-introducing into the vessel;
    e) introducing additional monomer into the recycle stream instead of polymerized monomer so that the ratio of the recycle stream is maintained; and f) removing the polymer product from the reactor. A method comprising steps.
  29.   29. The method according to claim 28, wherein the [alpha] -olefin comonomer has 3 to 15 carbon atoms.
  30.   30. A method according to claim 28 or claim 29, wherein the liquid phase and the gas phase are separately introduced into the reactor.
  31. 31. A method according to any one of claims 28 to 30, characterized in that the polymer product has a density of less than 0.910 g / cm3 and / or a melt index of more than 3 dg / min. Method.
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